by Asst. Prof. Dr.

Ekathai Wirojsakunchai
Mechanical Engineering Dept.
Kasetsart University

1
 Energy Balance for A Closed System
The first law cannot be proven mathematically, but no process in nature
is known to have violated the first law, and this should be taken as
sufficient proof.

Energy balance for any system

undergoing any process

Energy balance in the

rate form

Energy balance per

unit mass basis

Energy balance in
differential form
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 Examples of 1st Law Applications
Qin Qout = E
15 3 = 12 kJ

Soda @ 25C, Q = E = 0
Soda @ 15C, 8 J/s = E25C E15C
Soda @ 5C, 16 J/s = E25C E5C

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 1st Law for a Process
Therefore, 1Q 2 1W 2 E 2 E1

or Q W dE
where 1Q2 = The net heat transfer as the system undergoes from state 1 to 2
1W2 = The net work done during the same process
E1, E2 = The system energy at state 1 and 2
Types of Energy (E)
1. Mechanical Energy ()
i. Kinetic Energy (; KE) = (1/2).m.c2
ii. Potential Energy (; PE) = mgz

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 Internal Energy, U
2. Internal Energy (; U) is an extensive property. Normally, we
represent the internal energy in terms of small u which an intensive property
(u, = U/m). We can use the value of u to identify the phase
of pure substance, just like P-v-T, as we can see from Table B.1.1 and B.1.2.
Column u on in the left-hand side of column v.
We can use u to define phase of pure substance just like
v, thus
u<uf Compressed Liquid
u=uf Saturated Liquid
uf<u<ug Sat. Liquid-Vapor Mixture
u=ug Saturated Vapor
u>ug Superheated Vapor
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 Internal Energy, U (2)
The relationship of uf and ug is similar to that of v
u = uf+x.ufg (kJ/kg)
In sum, E U KE PE
dE dU dKE dPE
Q W dU dKE dPE

If Q and W equal to 0, E = 0 The energy of a system

remains constant if the system is isolated from its surroundings
1 2 1 2
E 2 E1 U 2 U 1 mc2 mc1 mgz 2 mgz1
2 2
1
1Q 2 1W 2 U 2 U 1
2

m c22 c12 mg z 2 z1
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 Other Forms of 1st Law
From eq. Q W = E (kJ)
o Per unit mass q w = e (kJ/kg)
dE
o On the rate form Q W (kW)
dt

Normally, we will not consider the effects of kinetic and potential

energy on the system (Since in Thermodynamics, the systems are
piston-cylinder, vessel, Turbine, Pump, and Heat Exchanger that have
no movement). Therefore, we can rewrite 1st law equation as follows.
Q 2 1W 2 U 2 U1
1

mu2 u1
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 Enthalpy, h
H is defined from the relationship of U, P, and V

H U PV (kJ )
h u Pv (kJ / kg )

Enthalpy (; H) is another thermodynamic property which is

similar to v and u. That is, it can be used to identify the phase of
pure substance. The relationship between h and x are as follows.
h h f x.h fg

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 Enthalpy (2)
The values of u and h are calculated based on the
reference point, i.e. In water table, B.1.1, the value of h
and u are equal to 0 at T=0.01C. Or for Ammonia and R-
12, the reference point of h and u that are equal to 0 is
at T=-40C. Therefore, the value of h and u can be
negative if the state is below the reference point.
In case of a compressed liquid water, the value of h and
u can be found from Table B.1.4. But for another pure
substance which dose not have a Compressed Liquid
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Table, we use h=hf@T+ vf@T(P-Psat)
 Specific Heat
Specific Heat (; c) is the energy that
make a unit mass has temperature rise of 1 degree
Specific Heat can be categorized into two types
Specific Heat at Constant Volume, Cv
Specific Heat at Constant Pressure, Cp
From 1st Law: Q - W = dU or Q = dU + W = dU + PdV
1. V=const.; 1 Q
cv
1 U u

m T v m T v T v
1 Q 1 H h
cp
2. P=const.; m T p m T p T p
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 Specific Heat (2)
We can define the specific heat based on the phase of pure
substance as follows
1. Gas; c u = The rate of change in internal energy with temp at constant volume
v
T v
h
c p = The rate of change in enthalpy with temp at constant pressure
T p

2. Solid or Liquid (Table A.3): cv=cp=const. since const. volume

and const. pressure are the same process
dh = du = cdT
h2-h1 = u2-u1 = c(T2-T1)
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 Internal Energy, Enthalpy, and Specific Heats of an
Ideal Gas
The conclusion of Joules experiment on Ideal Gases, u u (T )

Read T1 Read T2 = T1
Insulated water bath Insulated water bath

Valve is closed Valve is open

A B A B
air air air

H2O H2O

State 1: P1,A >> P1,B, T1 State 2: P2,A = P2,B < P1,A, T2 = T1

(Air inside vessel A, while vessel B is vacuumed) (Valve is now open, air flow from A into B and
finally, reaching equilibrium )
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 Internal Energy, Enthalpy, and Specific Heats of an
Ideal Gas (2)
From h = u+Pv = u+RT for Ideal Gases, h h(T )
Since u = u(T) for only an ideal gas, thus cv0 (subscript 0 refers to
cv for ideal gas)
u du
cv 0
T v dT

du cv 0 dT
dU mcv 0 dT
Similarly,
dh c p 0 dT
dH mc p 0 dT

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 Internal Energy, Enthalpy, and Specific Heats of an
Ideal Gas (3)
Notice From cv0 = du/dT and cp0 = dh/dT
1. cv0 and cp0 depends only on temperature
2
u u 2 u1 cv 0 (T )dT
2. 1
2
h h2 h1 c p 0 (T )dT
1

3. c p 0 cv 0 R or c p 0 cv 0 R
c p0
4. k (Specific Heat Ratio) = cv 0

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 Internal Energy Change of an Ideal Gas
We can calculate the value of (u2-u1) for an ideal gas via three
methodologies according to the value of specific heat as follows.
Method 1 cv0 is constant (Approximated Method)
u 2 u1 cv0 T2 T1

The value of cv0 in the above equation is at room temperature (300K),

which can be found from Table A.5
Method 2 cv0 is a function of temperature
T2 2
u 2 u1 cv 0 T dT

T1
c p0 R .1000d
1

The value of cp0 () is called Empirical Equation, which can be found

15 from Table A.6 where = T/1000
 Internal Energy Change of an Ideal Gas (2)
Method 3 cv0 is a function of temperature and using Table A.7.1, A.8
(Exact Method)
T
Define :
uT uT0 cv 0 (T )dT
T0
T2 T1

u 2 u1 uT2 uT1 cv 0 T dT cv 0 T dT

T0 T0

The value of u in the table comes from the integration of cv0 at T with
respect to T0. Thus, Method 3 give the best accuracy whereas
Method 1 is the least accurate. Method 2 is not in the test.
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 Enthalpy Change of an Ideal Gas
We can calculate the value of (h2-h1) for an ideal gas via three
methodologies according to the value of specific heat as follows.
Method 1 cp0 is constant (Approximated Method)
h2 h1 c p 0 T2 T1

The value of cp0 in the above equation is at room temperature (300K),

which can be found from Table A.5
Method 2 cp0 is a function of temperature
T2 2
h2 h1 c p 0 T dT c p 0 .1000d
T1 1

The value of cp0 () is called Empirical Equation, which can be found

17 from Table A.6 where = T/1000
 Enthalpy of an Ideal Gas (2)
Method 3 cv0 is a function of temperature and using Table A.7.1, A.8,
A.9 (Exact Method)
T
Define hT hT0 c p 0 (T )dT
T0
T2 T1

h2 h1 hT2 hT1 c p 0 T dT c p 0 T dT
T0 T0

h2 h1
Table A.9 : h2 h1
MW

The value of h in the table comes from the integration of cp0 at T with
respect to T0. Thus, Method 3 give the best accuracy whereas
18 Method 1 is the least accurate. Method 2 is not in the test.
 Enthalpy of an Ideal Gas (3)
Notice 1. In Table A.9 (N2-N, O2-O, CO2-CO, H2O-OH, H2-H, and
NO-NO2), the value of h is in kJ/kmol (reference point is at
298 K)
2. Table A.8 (N2, O2, CO2, and H2O) is Table A.9 but only h
is in kJ/kg (but the reference point is still at 0 K). The
table also gives the value of u for convenience.
3. h from Table A.8 and A.9 of the same gas must always
be the same value.
4. Table A.7.1 gives the value of u and h of Air in kJ/kg
(reference point is at 0 K)
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